Dehydrogenation catalyst



Patented Apr. 15, 1947 DEHYDROGENATION CATALYST Kenneth K. Kearby, Elizabeth, N. J., assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application March 13, 1943, Serial No. 479,144

1 Claim.

This is a continuation in part of my copending application Serial No, 456,267, entitled Dehydrogenation of hydrocarbons and catalysts therefor, filed August 26, 1942, now Patent No. 2,370,798.

This application contains a disclosure similar to that contained in the application of Kenneth K. Kearby filed February 14, 1942, and assigned Serial No. 430,873, now Patent No. 2,395,875.

My present invention relates to catalytic dehydrogenation of hydrocarbons, and more particularly, it relates to improved catalysts for dehydrogenating olefins and aralkyl hydrocarbons, and to methods for preparing the said catalysts.

My present invention is particularly adapted'to the dehydrogenation of low molecular weight olefin hydrocarbons having from 2 to 10, preferably 2 to 6, carbon atoms, but is also applicable to dehydrogenation of aralkyl hydrocarbons, such as ethyl and propyl benzene to form styrene and phenylmethyl-ethylenes and to convert isopropyl benzene to a methyl styrene.

Recently, processes designed to convert butene to butadiene have become of increased importance due to the fact that butadiene is an essential intermediate in one of the more important methods for the production of synthetic rubber-like materials.

In the production of diolefins from olefins by the catalytic dehydrogenation of mono-olefins, it is, of course, desirable to obtain as high a yield of the diolefin as possible per one passage of the butene thru the dehydrogenation zone, and as a corollary to this purpose, it is also a desideratum to this type of process to obtain as small an amount as possible of by-products. It is also desirable to conduct the dehydrogenation under such conditions that the fouling of the catalyst is minimized to as great an extent as possible. The efllciency of the catalyst is best measured in terms of per cent selectivity, which means the per cent of the total amount of initial material which undergoes conversion which is converted to the desired product. For example, if 50% of the initial material undergoes conversion of some sort, and 30% of the initial material is converted to the desired product, then the selectivity would be 60.

I have now discovered a new type of catalyst which when used under certain conditions in the dehydrogenation of hydrocarbons makes it possible to obtain substantially greater yields of the desired dehydrogenation product than can be obtained by the use of previously known catalysts. The nature of this new type of catalyst and the conditions under which it is used will be fully understood from the following description,

In the above referred to Kearby application there is disclosed a dehydrogenation catalyst which comprises magnesium oxide as a base material, iron oxide as an active ingredient, and a small amount of a promoter which consists of an alkali or an alkaline earth oxide. In addition, the catalyst may contain a small amount of a stabilizer which stabilizer may consist of an oxide, of a metal Of the right-hand side (transition series) of groups I, II, and III of the periodic system or certain non-acidic oxides.

As pointed out in the aforesaid prior Kearby application, the principal function of the promoter in these catalysts is to increase the dehydrogenating activity of the catalyst. The principal function ofthe stabilizer, when used, is to prevent the promoter from volatilizing or becoming inactive.

Now in my present application, I propose to use as a base, beryllium oxide, and this material should constitute the major portion of the entire catalyst composition. The following table gives the range of each component which may be used:

Parts by Component weight BeO 50-97 F9203... 3-50 Prom oter. 0. 5-15 Stabilizer 1-15 Among the alkali metal and alkaline earth oxides which may be used as promoters are the oxides of calcium, strontium and sodium, but potassium oxide is greatly superior.

However, I wish to point out that some of the desired conversion is obtained by omitting the promoter and the stabilizer and compounding the catalyst only from the base and the active ingredients.

The following stabilizing oxides give good results: Oxides of metals of the right-hand side (transition series) of groups I, II, and'III of the periodic system, particularly oxides of copper and silver; non-acidic transition oxides of chromium, manganese, cobalt and nickel; and non-acidic oxides of zirconium, cerium, lead, bismuth, and particularly A1203 and ThOz.

In place of the iron oxide in the above type of catalyst, oxides of chromium and manganese also form good catalysts. Nickel and cobalt oxides give less selective catalysts. Eliective catalysts are obtained with all of these active ingredib Component aga BaO 8 .1 Foa 20 K10- e CuO 5 The above catalyst may conveniently be prepared as follows:

Example soneo-nor-ezohscuo-smo A solution of 209 grams of ferric nitrate and 38.5 grams of copper nitrate in 1 liter of H20 was stirred into a suspension of 355 grams of hydrated -beryllium oxide (47.7% loss on ignition) in 2 liters of water. A solution of 170 grams of KzCOs in 200 cc. of water was added and the mixture stirred for 1 hour at 80-90 C. The precipitate was filtered, thoroughly washed, and mixed with a solution of 18.8 grams of KzCOa in 200 cc. of H20. The wet mixture was dried, heated for 3 hours at 1200 F., and pilled.

The above catalysts possess a high degree of selectivity to the dehydrogenation of normal butene to butadiene, the selectivity being of the order of 70-85%. g

In order to set forth the utility of my invention, the following description of a test in which butene-l was dehydrogenatcd to form butadiene when employing a beryllium oxide as base catalyst is set forth below:

A mixture of normal butenes (containing 95% of butene-Z) was passed for one hour at a rate of 800 volumes (normal temperature and pressure) per volume of catalyst per hour, with 5600 volumes of steam over the catalyst whose preparation was described in the above example, at a temperature of 1200 F. The amount of butene converted to butadiene was 29.2%, with a total conversion of 39% and a. selectivity of 75%.

At lower conversions of about 25-30%. selectivities of 80% can be obtained when the lower conversion is obtained by reducing the temperature or increasing the through-put.

In carrying out the process using catalysts of the type above described, the hydrocarbon, preferably with steam, is passed over the catalyst at a rate between 50 and 5000, preferably between 100 and 1000 volumes (measured at normal temperature and pressure) of hydrocarbon per volume of catalyst per hour. The ratio of steam to hydrocarbon is between 30:1 and 1:1,preferably from 8:1 to 4:1. The reaction chamber is maintained at a temperature between 1000' and 1600 F., preferably between 1100 and 1300 F. and under atmospheric, below atmospheric or above atmospheric pressure. The hydrocarbon which passes through the reaction zone unaffected may of course be recycled thereto.

The principal function oi. the steam is to dilute the hydrocarbon and thus reduce Y the partial pressurethereof in the reaction zone. At the same time, however, the steam performs another useful function in that it reacts with coke which may be deposited on the catalyst to form carbon oxides and hydrogen. The elimination of at least a portion of the coke in this manner tends to prolong the time the catalyst can be used before it requires regeneration. Thus the reaction portion of a, complete cycle of reaction and regeneration may be as long as 15, 25 or 50 hours or more although it is usually preferable in'operation to run for-periods of hour to 10 hours and then regenerate.

Regeneration of the catalyst may be effected by shutting oil the flow of hydrocarbon and passing steam, air, or a mixture or steam and air 7 through the catalyst mass while it is maintained at a temperature between 1100 F. and 1300" F. Following substantially complete removal of coke from the catalyst in this manner, the flow of hydrocarbon and steam may be resumed.

My present invention may be carried out either in the stationary bed type of operation or a fluid catalyst type of operation. In the former, the catalyst is contained in a case or reactor and the mixture of steam and hydrocarbon is simply forced through the material preferably being discharged into the top, forced through the catalyst, and withdrawn from the bottom. The catalyst is preferably in the form of pellets. pills, granules, and the like. In the fluid catalyst type of operation, the catalyst is in the form of a powder having a particle size of from 100 to 400 mesh and is discharged into the reaction zone from a standpipe together with the hydrocarbon to be dehydrogenated, and steam, the catalyst and vapors entering preferably at a point at the bottom I of the reactor and passing upwardly through a grid and forming within the reactor a dense phase suspension, that is to say. a suspension of catalyst in the gases of a concentration such that each cubic foot contains from 2 to 35 or more pounds of catalyst. This dense phase may be formed within the reaction zone above the grid by controlling the linear velocity of gases or vapors by maintaining it within the range of say to 8 to 10 ft./sec. Continuity of operation may be thus obtained and the catalyst may be withdrawn throughv a bottom draw-off pipe regenerated, if necessary, and returned preferably substantially uncooled through the aforementioned standpipe to the reactor. The precise details, however, of operating the reactor do not form an important aspect of my present invention and any known reactor adapted to provide good contact between the solid and gas may be employed.

To recapitulate, my present invention relates toimprovements of dehydrogenation catalysts, to the methods of preparing such catalysts, and is characterized briefly by the fact that I employ a beryllium oxide base in addition to iron oxide, and, usually an oxide of iron, chromium, manganese, cobalt or nickel, a small amount of a promoter and/or a stabilizer. An outstanding advantage of my invention is that I may carry out the dehydrogenation of a hydrocarbon in the presence of large quantities of steam without injuring the catalyst and thus I may greatly extend the life of catalysts since the presence of steam tends to retard the deposition of hydrocarbon contaminants upon the catalyst. Also, the presence of steam makes it possible to supp y the heat necessary for this highly endothermic reaction by the superheating of the said steam at oxide.

KENNETH K. KEARBY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Number Name Date Wulfl et a1 Jan. 1, 1935 Mark et a1 Mar. 8, 1938 Visser et a1. Feb. 3. 1943 Bosch et a1. July 29, 19l3 Tropsch Feb. 21, 1939 Groli et a1 Dec. 19, 1939 Pier et a1 Oct. 1, 1940 Grossklnsky et a1. Dec. 9, 1941 Chickinofi Mar. 30. 1943 FOREIGN PATENTS Country Date British Aug. 19. 1930 British Dec. 30, 1930 Swiss Sept. 16, 1930 Swiss Sept. 16, 1930 

